Almudena Gallego

Solvent‐Induced Delamination of a Multifunctional Two Dimensional Coordination Polymer

A coordination polymer is fully exfoliated by solvent-assisted interaction only. The soft-delamination process results from the structure of the starting material, which shows a layered structure with weak layer-to-layer interactions and cavities with the ability to locate several solvents in an unselective way. These results represent a significant step forward towards the production of structurally designed one-molecule thick 2D materials with tailored physico-chemical properties.

Electrical conductivity and luminescence in coordination polymers based on copper(I)-halides and sulfur-pyrimidine ligands.

The solvothermal reactions between pyrimidinedisulfide (pym(2)S(2)) and CuI or CuBr(2) in CH(2)Cl(2):CH(3)CN lead to the formation of [Cu(11)I(7)(pymS)(4)](n) (pymSH = pyrimidine-2(1H)-thione) (1) and the dimer [Cu(II)(μ-Br)(Br)L](2) (L = 2-(pyrimidin-2-ylamino)-1,3-thiazole-4-carbaldehyde) (2). In the later reaction, there is an in situ S-S, S-C(sp(2)), and C(sp(2))-N multiple bond cleavage of the pyrimidinedisulfide resulting in the formation of 2-(pyrimidin-2-ylamino)-1,3-thiazole-4-carbaldehyde. Interestingly, similar reactions carried out just with a change in the solvent (H(2)O:CH(3)CN instead of CH(2)Cl(2):CH(3)CN) give rise to the formation of coordination polymers with rather different architectures. Thus, the reaction between pym(2)S(2) and CuI leads to the formation of [Cu(3)I(pymS)(2)](n) (3) and [CuI(pym(2)S(3))] (pym(2)S(3) = pyrimidiltrisulfide) (4), while [Cu(3)Br(pymS)(2)](n) (5) is isolated in the reaction with CuBr(2). Finally, the solvothermal reactions between CuI and pyrimidine-2-thione (pymSH) in CH(2)Cl(2):CH(3)CN at different ratios, 1:1 or 2:1, give the polymers [Cu(2)I(2)(pymSH)(2)](n) (6) and [Cu(2)I(2)(pymSH)](n) (7), respectively. The structure of the new compounds has been determined by X-ray diffraction. The studies of the physical properties of the novel coordination polymers reveal that compounds 3 and 5 present excellent electrical conductivity values at room temperature, while compounds 1, 3, and 5-7 show luminescent strong red emission at room temperature.

Dynamic combinatorial chemistry in a solvothermal process between nickel(II), halides and organosulphur ligands

A dynamic combinatorial process has allowed the isolation of four new compounds produced in the direct solvothermal reactions of pyrimidine-2(1H)-thione (pymSH) or bis(2-pyrimidyl)disulfide (pym2S2) with nickel halides (chloride, bromide). The in situ cleavage of S–S, S–C(sp2) bonds generates the pyrimidinesulfide (pym2S) and pyrimidinetrisulfide (pym2S3) ligands and the formation of nickel complexes. In all cases, the in situ generated molecules behave as chelating terminal ligands, therefore no evidence of their potential bridging capability is available for Ni(II). The magnetic properties of the compounds indicate the presence of moderate antiferromagnetic interactions that become more intense as the number of bridging halides increases.

Structure and Properties of One-Dimensional Heterobimetallic Polymers Containing Dicyanoaurate and Dirhodium(II) Fragments

The synthesis and characterization of compound [Rh(2)(O(2)CEt)(4)(H(2)O)(2)] (1) and one-dimensional heterobimetallic polymers K(n){Rh(2)(O(2)CEt)(4)[Au(CN)(2)]}(n) (2) and K(n){Rh(2)(O(2)CMe)(4)[Au(CN)(2)]}(n)·4nH(2)O (3), constructed from dirhodiumtetracarboxylato units, [Rh(2)(O(2)CR)(4)](+), and dicyanoaurate, [Au(CN)(2)](-), fragments are described. In both compounds 2 and 3 the resulting polymeric chains are nonlinear and have in common similar structural parameters, although the solid state supramolecular arrangement is very different. These structural differences explain the fact that complex 2 displays aurophilic interactions while this type of interactions are absent in complex 3. As a result, compound 2 shows rich blue luminescent properties whereas compound 3 is not luminescent. The electrical conductivity in solid state of compounds 2 and 3 is also studied.

Properties of self-assembled nanostructures: general discussion

Javier Reguera, Edward Malachosky, Matthew Martin, Moritz Tebbe, Bruce Law, Lucio Isa, Helmuth Moehwald, Yangwei Liu, Fernando Bresme, Dhanavel Ganeshan, Christopher Sorensen, Suvojit Ghosh, Andreas Fery, Petr Kral, Asaph Widmer-Cooper, Christina Graf, Almudena Gallego, David Schiffrin, Brian Korgel, Gunadhor Okram, Subramanian Sankaranarayanan, Yifan Wang, Toshiharu Teranishi, K. Michael Salerno, Sean McBride and Xiao-Min Lin